Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals

Alexandre M. Boulet, Eric D. Walter, Dwight A. Schwartz, Gary J. Gerfen, Patrik R. Callis, David J. Singel

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Electron-magnetic resonance spectroscopy and computational studies of the cysteine cross-linked tyrosyl radical in apogalactose oxidase have led to conflicting ideas regarding spectral assignments and protein-environment effects. We report DFT calculations on model radicals that clarify these issues. Calculated Fermi contact interactions do not resolve the ambiguity in spectral assignments; better insight is provided by the anisotropy of the hyperfine interactions and the systematic effects of thioether substitution. DFT results on model systems do not account for salient properties of the apogalactose radical. This inadequacy suggests that the protein environment exerts significant effects on the electronic structure of the radical.

Original languageEnglish (US)
Pages (from-to)108-114
Number of pages7
JournalChemical Physics Letters
Volume331
Issue number1
StatePublished - Nov 24 2000

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Sulfides
Discrete Fourier transforms
Electronic structure
Electron resonance
Magnetic resonance spectroscopy
electronic structure
Electron spectroscopy
Cysteine
Oxidoreductases
Proteins
Anisotropy
Substitution reactions
interactions
environment effects
proteins
oxidase
cysteine
magnetic resonance spectroscopy
ambiguity
electric contacts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Boulet, A. M., Walter, E. D., Schwartz, D. A., Gerfen, G. J., Callis, P. R., & Singel, D. J. (2000). Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals. Chemical Physics Letters, 331(1), 108-114.

Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals. / Boulet, Alexandre M.; Walter, Eric D.; Schwartz, Dwight A.; Gerfen, Gary J.; Callis, Patrik R.; Singel, David J.

In: Chemical Physics Letters, Vol. 331, No. 1, 24.11.2000, p. 108-114.

Research output: Contribution to journalArticle

Boulet, AM, Walter, ED, Schwartz, DA, Gerfen, GJ, Callis, PR & Singel, DJ 2000, 'Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals', Chemical Physics Letters, vol. 331, no. 1, pp. 108-114.
Boulet AM, Walter ED, Schwartz DA, Gerfen GJ, Callis PR, Singel DJ. Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals. Chemical Physics Letters. 2000 Nov 24;331(1):108-114.
Boulet, Alexandre M. ; Walter, Eric D. ; Schwartz, Dwight A. ; Gerfen, Gary J. ; Callis, Patrik R. ; Singel, David J. / Electronic structure and hyperfine interactions in thioether-substituted tyrosyl radicals. In: Chemical Physics Letters. 2000 ; Vol. 331, No. 1. pp. 108-114.
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